Date of Award

1995

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Andrew W. Maverick

Abstract

Following our studies of cofacial binuclear transition metal complexes, such as $\rm Cu\sb2(XBA)\sb2$ (see below), we became interested in the synthesis of a more rigid ligand, ABIH$\sb2$ which contains a 1,8-anthracene bridge. This new ligand, whose chelating moieties are constrained to be cofacial, should enable us to obtain a wide variety of cofacial bimetallic complexes such as 1, with controllable environments around the metal centers, for synthesis of multi-metal redox active catalysts.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI). Three routes have been pursued to synthesize the anthracene-based ligand. Using organometallic derivatives of 3,5-dimethylisoxazole as acetylacetone synthons, the bis($\beta$-ketoenamine) ABIH$\sb2$ was successfully obtained. Two novel cofacial binuclear complexes 1, with ML$\rm\sb{n}$ = $\eta\sp4$-1,5-cyclooctadiene)iridium and dicarbonylrhodium, have been synthesized. They are the first members of a new family of cofacial bimetallic complexes that may provide new models for redox-active enzymes, such as cytochrome oxidase.

Pages

120

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